Manufacture and use of dyestuffs



Patented Sept. 8, 1936 UITED STATES PATENT OFFICE MANUFACTURE AND USE OFDYESTUFFS George Holland Ellis and Frank Brown, Spcudon, near Derby,England, assignors to Celauese Corporation of America, a corporation ofDelaware 13 Claims.

This invention is a divisional of U. S. application Ser. No. 655,614filed 7th February, 1933, and relates to the colouration of celluloseester and ether materials.

The amino and simple alkylamino derivatives of anthraquinone, forexample 1:4-dimethylamino anthraquinone, are of value for thecolouration of cellulose ester and ether materials in that by their aidit is possible to secure, by direct dyeing methods, shades of bluedifficult to secure by means of other dyestufis. Many of these dyeings,however, while reasonably fast to most of the agencies which textilematerials are commonly required to withstand, sufier from a lack ofresistance to the combined action of light and acid, for instancecombustion products of coal gas. This lack of resistance is particularlyobjectionable in that in general it involves a considerable change inshade towards red and not merely a reduction in the intensity of thedyeing. It may be said that in this respect no really satisfactorydirect blue dyestufi for cellulose ester and ether materials is as yetavailable. Thus, many arylamino anthraquinones, though ofiering veryconsiderable resistance to the action of acid fumes in the presence oflight, have such low amnity for the material as to render themcommercially valueless except possibly for the production of paleshades. l-oxy-i-phenylamino anthraquinone for instance, is extremelyresistant to acid fading, but is very 'red in shade and at the same timeis lacking in aflinity.

We have now found that derivatives of anthraquinone containing in onea-position a hydroxyl group, in a second a-position an amino ornonaromatically substituted amino group and in a third a-position anarylamino group, these substituents being the sole substituents in theanthraquinone nucleus, constitute very valuable colcuring matters forcellulose ester and ether materials, and the present invention consistsin the colouration of cellulose acetate or other organic derivative ofcellulose with these anthraquinone derivatives.

The dyestuffs employed for the colouration of organic derivatives ofcellulose in accordance with the present invention may be represented bythe following formula:-

wherein the anthraquinone nucleus A has as sole substituents, in threea-DOSitlODS the groups X, Y and Z, of which X represents a hydroxylgroup,

Y an aryl substituted amino group, and Z a free amino group or anon-aromatically substituted amino group, i. e. an amino groupsubstituted only by aliphatic or other residues such that carbon of anaromatic nucleus if present therein is not directly attached to theamino nitrogen. By means of dyestufis of this series, more particularlyby dyestuffs of the above formula in which the arylamino group is in apara-position to either the hydroxyl group or the other amino group,especially the latter, blue shades of exceptional resistance to theusual agencies may be obtained. For example1-amino-4-pheny1amino-5-hydroxy anthraquinone dyes cellulose acetatematerial in pure blue shades of excellent fastness both to light and tolight in the presence of acid fumes such as combustion products of coalgas. Coupled with these valuable properties the dyestufi displays verygood afiinity for the material. By shading with small quantities of redand yellow dyestuffs very desirable navy blue shades may be obtained.

The aryl substituent oi the arylamino group may be of any desiredcharacter, for example of the benzene, naphthalene or other series, butis preferably of the benzene series. It may be substituted in anydesired manner. Thus, for example, it may contain alkyl, hydroxy,alkoxy, amino, halogen or other substituents. Special reference may bemade to the presence of acidylamino groups, which may increase theafiinity of the dyestuflf for the material as described in U. S.application Ser. No. 655,617 filed 7th February, 1933. Again, increasedaflinity may be innparted by the presence of an alkyl group or othersubstituent in the meta-position to the amino group, as described in U.S. application Ser. No. 665,513 filed 7th February, 1933, and alkyloxygroups especially in the ortho-position to the amino group may bepresent, whereby a still further increase of resistance to acid .fadingmay be secured (see U. S. application Ser. No. 655,616 filed 7thFebruary, 1933). The second hydrogen atom of the aryl substituted aminogroup may also be substituted, for example by means of an alkyl or otheraliphatic residue. When present, substituents oi the non-aromaticallysubstituted amino group of the anthraquinone derivatives may be of anydesired character provided that the amino nitrogen is not directlyattached to carbon of an aromatic nucleus of the substituent. Asexamples of suitable substituents mention may be made of methyl or ethylor other alkyl groups, substituted alkyl groups, for examplehydroxyethyl, hydroxy-propyl or -chlor-p-hydroxypropyl, aliphatic acidylgroups for example acetyl, hydrogenized aromatic residues for examplecyclo-hexyl or substituted cyclo-hexyl groups, and aralkyl groups orhydrogenized aralkyl groups for example benzyl or hydrogenized benzylresidues. If desired the substituent may be united at two points to theamino nitrogen so as to form a heterocyclic residue, as an example ofwhich may be mentioned the piperidyl group. All of the abovesubstituents are in effect aliphatic in character and are so referred toin the appended claims. Two separate substituents may be present in theamino group in question, if desired. Most satisfactory results have beenobtained when the amino group is either unsubstituted or substitutedonly by methyl, ethyl or other aliphatic residue of relatively lowmolecular weight. The dyestuffs applied to the materials are preferablyunsulphonated.

The colouring matters may be applied to textile materials in solutionwhere sufiiciently soluble, in aqueous suspension, or after beingbrought into colloidal form.

For convenience in application, the new colouring matters may beconverted into concentrated or other preparations, whether liquid orsolid or semi-solid, in which the colouring matters are present incolloidal, dispersed, or other finely divided conditions. Suchpreparations are included within the scope of the invention and may beprepared for example, by grinding (e. g. in colloid mills), bydissolving in a solvent and mixing with water containing or notcontaining protective colloids and/or dispersators, or by treatment withdispersing agents whether alone or in the presence of protectivecolloids and/or liquids, e. g. water.

As examples of dispersing agents or protective folloids mention may bemade of the followrig:-

Sulphoaromatic fatty acid compounds, e. g. sulpho-benzene palmitic acidcompounds (see U. S. Patent No. 1,694,413).

Sulphoaromatic ricinoleic acid compounds, e. g.sulpho-naphthalene-ricinoleic acid, (see U. S. Patent No. 1,840,572)

Naphthenic acids or other carbocylic compounds containing salt-forminggroups or salts of such acids or compounds (see U. S. Patent No.1,618,414)

Sulphonated oil compounds, e. g. Sulphonated castor oil.

Sulphuric esters of higher aliphatic alcohols.

Furfural-naphthalene sulphonic acid compounds (see U. S. Patent No.1,928,647

Resino-naphthalene sulphonic acid compounds (see U. S. Patent No.1,959,352).

Formaldehyde naphthalene sulphonic acid compounds.

A1kyl-, cycloalkyl-, and aralkyl-naphthalene sulphonic acids.

Sulphite cellulose waste liquor or its constituents or products oftransformation, e. g. lignln sulphonic acid compounds.

sulphonic acid compounds of mineral oils, tar oils, brown coal tar oils,and the like, and their products of condensation with alcohols.

Sulphonic acid compounds of distillation residues of benzaldehyde.

Carbohydrates including gmns.

Glue and gelatine.

By addition of or dilution with water, the aforesaid preparationscontaining unsulphonated colouring matters yield aqueous suspensions orcolloidal solutions which may be directly emaosaerr ployed for thecolouration of cellulose acetate or other organic substitutionderivatives of cellulose.

The colouring matters may be applied to the materials in any desiredmanner, for example by dyeing or other method of uniform application, orby printing, stenciling or other method of local application. Forprinting cellulose acetate goods the dyestuff may be applied inconjunction with thickening agents or with swelling agents for thecellulose acetate, e. g. methylated spirits. If desired the newcolouring matters may be employed for the colouration of stannouschloride discharges in the manner described in U. S. Patent No.1,949,413.

As examples of cellulose esters and ethers which may be coloured inaccordance with the present invention reference may be made to celluloseacetate, formate, propionate or butyrate or the products obtainable bytreating alkalized cellulose with esterifying agents, or the ethyl,benzyl or other ethers of cellulose. The dyestuffs may also be appliedto mixed materials comprising one or more of the aforesaid celluloseesters or ethers in admixture with other textile fibres, for examplewool, silk or other animal fibres, or cotton, regenerated cellulose orother cellulosic materials. Such other fibres may be coloured by thesame dyestuffs as the cellulose esters or ethers when they possess therequisite amnity, or they may be coloured either in the same ordifferent shades by means of other dyestuifs, either before, after orsimultaneously with the colouration of the cellulose esters or ethers.

The invention is illustrated but not limited by the following example:--

Example To dye 10 kilograms of cellulose acetate knit fabric a blueshade:

1 kilogram of a paste consisting of one part of finely divided1-amino-4-anilido-5-oxy-anthraquinone, 6 parts of water and 3 parts ofTurkey red oil (50%) is heated to the boil with 10 litres of 2.5 g. p.l. soap solution with stirring, and strained through a filter cloth intoa dye-bath containing 300 litres of 2.5 g. p. l. soap solution. Thepreviously scoured cellulose acetate fabric is now entered in rope form,and dyeing commenced cold or luke warm, the temperature being raisedslowly to C. and maintained thereat for 1 hours or till the requisiteshade is achieved. The goods are now washed off thoroughly and dried orotherwise treated as desired or requisite.

For printing cellulose acetate goods the dyestufif paste is suitablydiluted and thickened with a gum thickening paste which may also containswelling agents for the cellulose acetate, e. g. methylated spirits.Printing, drying, steaming, etc. may then be efiected according to knowntechnique.

What we claim and desire to secure by Letters Patent is:-

1. Process for the colouration of materials comprising an organicderivative of cellulose, which comprises applying thereto ananthraquinone compound of the general formula:-

li y

wherein the anthraquinone nucleus A has, as sole substituents, in threea-positions the groups X, Y and Z, of which X represents a hydroxylgroup, Y an arylamino group and Z a group selected from the classconsisting of free amino groups and aliphatically substituted aminogroups.

2. Process for the colouration of cellulose acetate, which comprisesapplying thereto an anthraquinone compound of the general formula:-----and aliphatically substituted amino groups.

3. Process for "the colouration' of materials comprising organicderivatives of cellulose, which comprises applying thereto a1-amino-4-arylamino--hydroxy-anthraquinone.

4. Process for the colouration of cellulose acetate, which comprisesapplying thereto a iamino-4-arylamino-5-hydroxy-anthraquinone.

5. Process for the colouration of materials comprising organicderivatives of cellulose, which comprises applying thereto a1-allry1amino-4- arylamino-5-hydroxy-anthraquinone.

6. Process for the colouration of cellulose acetate, which comprisesapplying thereto a l-alkylamino-4-arylamino-5-hydroxy-anthraquinone.

7. Process for the colouration of cellulose acetate,which comprisesapplying thereto a 1-amino 4-phenyl-amino-5-hydroxyanthraquinone.

8. An organic derivative of cellulose coloured with an anthraquinonecompound of the general formula:-

wherein the anthraquinone nucleus A has, as sole substituents, in threeor-POSlt-IODS the groups X, Y and Z, of which X represents a hydroxylgroup, Y an arylamino group and Z a group selected from the classconsisting of free amino groups and aliphatically substituted aminogroups.

9. An organic derivative of cellulose coloured with a1-amino-5-hydroxy-anthraquinone substituted in the 4-position by anarylamino group of the benzene series.

10. An organic derivative with1-amino-4-phenylamino-5-hydroxy-anthraquinone.

11. Cellulose acetate coloured with a l-amino- 5-hydroxy-anthraqulnone,substituted in the 4- position by an arylamino group of the benzeneseries.

12. Cellulose acetate coloured with 1-amino-4-phenylamino-5-hydroxy-anthraquinone.

13. Cellulose acetate coloured with a i-aliphaticallysubstituted-amino5-hydroxy-anthraquinone substituted in the 4-positionby an arylamino group of the benzene series.

GEORGE HOLLAND ELLIS. FRANK BROWN.

of cellulose coloured

